Basic bismuth compound of camphocarbonic acid



water according to the following reaction:

Patented Aug. 8, 1933 v .i

unirso STATES PAT i LA BASIC BISMUTH COMPOUND 01* CAMPHO- CARBONIC ACIDGeorge W. Baiziss and Le Roy W. Clemence,

Philadelphia, Pa", assignors to Abbott Laboratories, North Chicago,

Illinois 111., a Corporation of no Drawing; ADPlicationMay 19.1930Serial 110.453.2354 I 3' Claims. (01. 260-11) 7 Our invention relatesgenerally to bismuth compounds of campho-carbonic (campho-carboxylic)acid, and relates more particularly to a basic compound thereof.

A particular object of our invention is to produce a new combination ofbismuth with camphocarboxylic acid which contains a comparatively highpercentage of bismuth, is oflowtoxicity, and is therapeutically active,particularly in the treat- 10 ment of spirochetic infections. 7

Various compounds of bismuth with camphocarboxylic acid have beendiscussed in the literature. Thus, Marius L. Picon (Chem. Abstracts,Sept, 1929, p. 4536, French Patent No. 657,694,

.15 Journal de Pharmacie et ChimiefSept 1928) mentions the preparationofa, neutral bismuth campho-carbonate obtained by the action ofcampho-carboxylic acid (campho-carbonic acid) on "anhydrous BizOa' inthepresence of traces of 6C1oH15O.COOH+Bi2O3 in water medium 2(C1oH150.COO) aBi+3H2O We have made the astounding discovery that byemploying large quantities of waterin reacting upon campho-carboxylicacid, or a salt thereof, with a bismuth salt, particularly in aglycerinewater medium, we are enabled to obtain a basic campho-carbonateof bismuth. For example, by

reacting upon sodium campho-carbonate ,,with I neutral bismuth nitratein a 1: 1 glycerine-water medium, as described below, our new basiccampho-carbonate of bismuth is obtained according to the followingreactions:

scmn ocoom Burma), in g1 cerine-water medium-o The basic bismuthcompound indicated above has a bismuth content of between 39% and 40%,calculated as metallic bismuth. The value of this compound in comparisonwith that obtained by Picon referred to above may be readily appreciatedwhen it isnOted'that Piconsbismuth product contains only about 25% ofbismuth, according to his own calculations. This higher bismuth contentof our product, together with low toxicity and high therapeutic value,

washed with two gallons .oi'water.

makes our basic campho-carbonate of bismuth of high value in thetreatment of spirochetic infections. Our improved product is alsosoluble in oils and fats. s

' The following example 100 grams of campho-carboxylic acid(camphocarbonic acid) are dissolved in 700 cc. of dis- .7

tilled water at 50 C. with the aid of 50 cc. of l 40% NAOH solution. Thesolution is filtered and .750 cc. of glycerine are added and cooled at20 C. 5"

, 67.5 grams of neutral bismuth nitrate Bi(NO3) 3 are dissolved in 250cc. of glycerine and cc." water at 40 0., cooled at 20? C. and. added ina slow stream to the acid. l q I Stir for one hour andfllter. Theprecipitate is washed with 400'cc. of 1:1 glycerine, removed from thefunnel, suspended. in 100000. or 1:1 glycerine, stirred for one hour,filtered v and The precipitate is again suspended in five gallons ofwater, mixed thoroughly, filtered and washed with water until there isno test for muth in the washings- It is driedin vacuo. 7,

To purify, this product isdissolved in methy ble;' filter off anyinsoluble matter and precipitate with ten volumes of water. Filter,washwith water, anddryin vacuo. J 1 v As indicated above, our basicbismuth product is believed to have the constitution ommiogooo 00mm I I/Bi O-Bi I 1 omnuoooo on.

This conclusion issupported by quantitative I experimental results. i

' We ascribe the'obtaining of our new bismuth compound containinga highpercentage of bismuth .to hydrolysis in the midst of the reaction,

due to the presence of a large quantity of water which acts on thebismuth saltin statu nascendi. Inorder to insure the formation of thedesired product, the precipitate is flnally dissolved in 100 methylalcohol and reprecipitated with a large quantity of water, as indicatedabove.

Various modifications may doubtless be made in our invention withoutdeparting from the spirit thereof, and hence we do not wish tobe limitedto thespecific procedure outlined or uses mentioned, but wish the scopeof our invention to be determined entirely from the-appended claims,which I are to be interpretedas'broadly as is consistent with the stateof. the art; f

We claim as our invention: 7 3. A basic bismuth salt having theprobable 1. A bismuth campho-carbonate containing formula: 7 from 39% to40% of bismuth. 01011150000 000.com

2. A bismuth 'campho-carbonate having two 5 atoms of bismuth in themoleeuleifor evei y three 7 C 0 v 7 campho-carboxylic (campho-caibonic)acid rad- GEORGE RAIZISS V icals. v v V i V LE ROY W. CLEMENCE.

